EP1681551A1 - Method and device for measuring the number concentration and average diameter of aerosol particles - Google Patents

Abstract

Aerosol particle number concentration measurement involves electrically charging an aerosol by diffusion charging, to create charged aerosol particles, for making measurement of a diffusional precipitator current. An influence current arising in a diffusional precipitator is compensated. The compensation of the current includes measuring an influence current in an additional electrode. The precipitator is a plate precipitator. An independent claim is also included for a device for measuring the number concentration and the average diameter of particles of an aerosol.

Description

The invention relates to a method and a device for measuring the number concentration and / or the mean diameter of suspended in a carrier gas particles. It also relates to a method for measuring the amount of elemental carbon in an aerosol.

Particles suspended in carrier gases (aerosols) play an essential role in the atmosphere, the breathing air and in many technical processes, for example in the emissions from internal combustion engines. The particles are often referred to as suspended dust or suspended particles. An important task is to measure the concentration of the particles by measurement. Particles in the size range less than 10 microns in diameter can be inhaled by humans and can have a negative impact on health. Recent research shows that the usual protective mechanisms of humans, especially for nanoparticles <100nm, are no longer effective. Nanoparticles are mainly produced in combustion processes such as car engines, coal power plants, wood heating etc.

Previous standards and guidelines usually give the particle concentration in the form of the particle mass per unit volume of the aerosol, for example in micrograms per cubic meter or in emissions of motor vehicles in mass per distance traveled or energy delivered (μg / km, μg / kWh). The particle loading thus specified practically only captures particles larger than about 0.1 microns, since the smaller ones, which can occur in high concentration, are not significant in terms of mass. Measuring methods that can detect small particles with corresponding weighting are therefore of topical importance. The focus is on a measurement of the particle number concentration. This is also required, for example, in new proposals from a European Commission of Experts on the limit value of diesel engine emissions. The size range of interest ranges from a few nanometers to a few hundred nanometers in the case of diesel particles. Even larger particles have no significant influence on the number concentration.

Today, almost exclusively condensation nucleus counters are used to measure particle number concentration (see, for example, Aerosol Measurement, Principles, Techniques and Applications, PA Baron and K. Willeke, Wiley, New York, 2001). The particles are brought into an environment with a supersaturated vapor (ia butanol vapor). The vapor condenses on the particles, causing them to grow so far that they can then easily be detected by measuring the light scattering. The counting of the light flashes of the individual particles allows a direct concentration determination. This method is very sensitive, it can also be extremely low concentrations are measured, but it requires in particular a very accurate maintenance of the temperatures in the generation and condensation of the supersaturated vapor. On the one hand, this makes them expensive and, on the other hand, dependent on the ambient conditions.

Also, when size information is required, systems based on mobility analysis are mainly used to measure the drift velocity of charged particles in an electric field. Most widely used is the scanning mobility particle sizer (SMPS, Wang, SC and RC Flagan: Scanning electrical mobility spectrometer, Aerosol Sci., Technol ., 13, 1990, 230-240). It has a relatively good accuracy, but a size spectrum measurement takes about 1-2 minutes. For 1-2 years, there are novel devices based on a similar principle, but have a time resolution of - 0.1-1s have (EEPS of TSI, DMS of Cambustion). These devices are big, heavy and expensive.

A diffusion-based device for measuring size distributions has recently been proposed (EP 1 156320 A1). Here, the particles are first charged with a diffusion charger and then separated in several stages by diffusion separators according to their size and electrically measured. With this measuring principle, size distributions of particles and thus also information about the number of particles in each size class can be determined. However, the apparatus is relatively expensive, and the evaluation of measurements is delicate.

Another important parameter for the assessment of the health hazard is the elemental carbon value, ie the total amount of elemental carbon present in particulate matter. This is because the harmfulness of the particles is primarily attributable to the carbon, which is usually present in the form of polycyclic aromatics. It has already been proposed to use the principle of photoelectric charging for the measurement of the number of charged particles with polycyclic hydrocarbons on the surface. From this, however, the total amount of elementary carbon is not readily derivable.

It is an object of the present invention to provide a method and a device for measuring the particle concentration or particle number and / or the average particle size, which overcomes the disadvantages of existing methods and which in particular enables rapid measurements with a comparatively less complex apparatus. Another object of the invention is to provide a method which enables the measurement of an elemental carbon value.

According to the invention, particles of an aerosol are first charged in a diffusion charger, for example, unipolar. Subsequently, they are passed through a diffusion separator, in which a part of the particles is deposited. The separated current is measured and a value for the number concentration is determined from the current.

The current generated in a diffusion separator of charged aerosol particles is hereinafter called "diffusion deposition current".

It is a realization of the invention that the relatively simple diffusion deposition current to be measured represents a measure of the particle number concentration. This for the following reasons

wobei K eine Funktion der Partikelgrösse ist.The average charge q̅ obtained by the particles in the diffusion charger is proportional to the attachment cross-section K of the particles: $$\tilde{q}\alpha K$$

where K is a function of particle size.

The probability that a particle is deposited in the diffusion separator depends on the diffusion constant D of the particles. This in turn is, to a good approximation, inversely proportional to the deposition coefficient K (according to A. Keller, M. Fierz, K. Siegmann, and HC Siegmann, and A. Filippov, J. Vac. Sci., Technol. A 19.1 2001, 1-8 ). $$D\alpha K^{-1}$$

The diffusion deposition current I caused by the deposited particles in the diffusion separator is measured. It is determined by the product of deposition probability, particle charge and particle concentration N, that is: $$I\alpha D\cdot \tilde{q}\cdot N\alpha K\cdot K^{-1}\cdot N\alpha N$$

The two size-dependent factors compensate each other, the diffusion deposition current depends only on the particle concentration and can thus be used according to the invention as a measure of the particle concentration.

The diffusion charger may, for example, be a unipolar diffusion charger. It may have an electrically shielded area with a high voltage field in which ions are generated. These flow through openings in the electrical Shielding (this is, for example, designed as a grid) in an area traversed by the aerosol.

In a particularly preferred embodiment of the invention, a single diffusion separator is used. In such a case, the surfaces on which particles are deposited and thereby contribute to a diffusion current are electrically connected to each other. So it is only an ammeter for detecting the diffusion current necessary. As i.a. Less preferred alternative can also be several electrically parallel surface areas (ie the surface areas are, for example, each provided with an electrometer, and the measured values of these are added, possibly after a calibration adjustment) or in parallel (ie by different aerosol shares) traversed surface areas each with be connected to an electrometer. In contrast to the prior art known from EP 1 156 320, where information about the number concentration can optionally be determined indirectly via the size distribution, however, the method according to the invention does not require a plurality of diffusion separators arranged in series behind one another. The inventive method therefore allows the use of a relatively simple apparatus for the determination of the number concentration.

The diffusion separator can, as is known per se, be designed as a plate separator, grate separator or tube separator. Combinations of these principles are also conceivable, for example. The diffusion separator can initially have a plate construction and then electrically connected to a grid or pipe arrangement; Other combinations are conceivable.

If particle concentration and / or size vary greatly during transient processes, the stream of charged particles that form the diffusion separator will also change reach, vary accordingly. In addition to the desired flow of deposited particles, these fluctuations cause an influent flow which interferes with the measurement. In order to compensate for this, a device for measuring the influence can be used in addition to the diffusion separator. Then only the Influenzstrom is measured. This can then be subtracted from the signal of the diffusion separator if necessary after a correction of the time delay with which the particles arrive in the two units and multiplication with a correction factor which compensates for different sensitivities. In this way, the Influenzstrom can be compensated.

The device for measuring the influence can be connected upstream or downstream of the diffusion separator in a serial arrangement. Alternatively, it may be arranged in parallel, i. each a defined proportion of the aerosol is fed to the diffusion separator and the Influenzmesseinrichtung.

Of course, "parallel" here and throughout the document is not to be understood geometrically, but refers to the way in which the individual devices are arranged with respect to the flow or how they are electrically connected.

The influential measuring device may look similar to the diffusion separator itself, but may not include separator plate tubes or grids. It has, for example, the same geometric shape as the diffusion separator, wherein the dimensions (for example, the extent in the direction of flow or the absolute size) need not be identical. The electrode of the influencing measuring device can be essentially set to zero potential or have the same electrical potential as the diffusion separator.

An influence current measurement of the type described above can also be used in connection with measurements other than the determination of the particle number concentration by means of diffusion deposition, provided that currents generated in a transient process (ie a process with non-stationary measured values) are measured by deposition of charged aerosol particles on electrodes. Examples thereof are measurements of the particle size distribution as disclosed in EP 1 156 320, measurements by means of impactors or measurements by means of differential mobility analyzers DMA. Such measurements are based on the fact that an aerosol with charged particles flows through a gas-conducting arrangement and - if necessary under the influence of physical and / or chemical effects - a proportion of the charged particles is deposited on separation surfaces connected to a first electrode. They are characterized in that a second electrode is present, which is preferably configured similar to the first electrode, but has no Abscheideflächen. The second electrode is upstream or downstream of the first electrode in the flow direction, or the electrodes are arranged in parallel as explained above. Incidentally, as in the aforementioned embodiment of the invention, it is not necessary for the second electrode to be at a specific potential; For example, it may be at zero potential or have the same potential as the first electrode.

According to a preferred embodiment of the invention, information about the particle size is determined in addition to an approximate value for the particle number concentration. Namely, the average particle charge in a wide range is, to a good approximation, proportional to d ^x , where d is the particle diameter and the exponent x is about 1.2. This means that the total charge concentration q _tot , which the particles carry, is proportional to Nd ^x . This total charge concentration can be determined by depositing all the particles in a filter and measuring the current I _tot that they cause there.

Thus, if both a diffusion separator and a filter are used, one obtains a current I which is proportional to N and a current I _tot which is proportional to Nd ^x . The particle diameter d can thus be determined from the quotient of the two streams. It is true that: $$d=c\cdot {\left(\frac{I_{\mathrm{dead}}}{I}\right)}^{\raisebox{1ex}{$1$}\!\left/ \!\raisebox{-1ex}{$x$}\right.}$$

The proportionality constant c can be determined by calibration or approximately calculated with known device geometry. If not only a particle size but a more or less broad size distribution is obtained, the determination of d results in an average particle diameter. If the filter is operated behind the diffusion separator to measure I _tot (ie the aerosol or portions thereof flow through or flow through) In order to obtain the total current I _tot , in order to measure the current measured in the filter, the diffusion separation current I measured in the diffusion separator must be added to a serial arrangement in succession, the diffusion separator and the filter). With this arrangement, number concentration and average diameter can be determined. Alternatively, a parallel arrangement is conceivable, where ever a defined proportion of the aerosol to be characterized is directed through the diffusion separator or the filter.

As already mentioned, the relationships described above are approximate. Upon closer inspection, there is some size dependency. The determination of the magnitude of the currents I and I _tot allows at least partial compensation of this size dependence. In addition to the additional size information can therefore also the accuracy of Number concentration determination can be improved if I _{dead is} also measured. For example, an experimentally determined size dependence may be considered.

According to a particular embodiment of the invention, the average diameter obtained in the measurement method is used to determine an elementary carbon total amount. For this purpose, a portion of the aerosol to be characterized in addition to the inventive measurement with diffusion charging, diffusion deposition and total charge concentration measurement also photoelectrically charged and the photoelectric charge per unit time measured. This happens in a parallel measurement string. From a to be characterized aerosol stream so a partial flow through a first measuring strand with diffusion charger and Diffusionsabscheider - and possibly other measuring devices, eg. For measuring the influence - passed, while another partial flow through a second measuring string with photoelectric charger and apparatus for measuring the total charge concentration - For example. Aerosolelektrometer - is passed.

• Wie an sich bekannt ist, wird die Photoemissions-Aufladeeffizienz in erster Linie von der Menge des vorhandenen Kohlenstoffs bestimmt. Die Photoemissionsaufladung korreliert demnach gut mit der Elementarkohlenstoffmenge.
• Es wurde experimentell gefunden, dass der Aufladefaktor von der Partikelgrösse abhängt, wenn eine feste Kohlenstoffmenge in Partikelform dargestellt und in einem Trägergas suspendiert wird. Die Abhängigkeit von der Partikelgrösse ist monoton.

The measurement in the first measuring string makes it possible, as stated above, to determine a mean diameter. This average diameter can be used to determine an elemental carbon value from the result of the photoemission measurement. This due to the following considerations and relationships:

• As is well known, the photoemission charging efficiency is determined primarily by the amount of carbon present. The photoemission charge correlates well with the elementary carbon amount.
• It has been found experimentally that the charging factor depends on the particle size when a solid amount of carbon is shown in particulate form and suspended in a carrier gas. The dependence on the particle size is monotone.

• A. Bestimmen eines mittleren Partikeldurchmessers der im Aersosol suspendierten Partikel
• B. Photoelektrisches Aufladen von Aerosolpartikeln
• C. Bestimmen einer Gesamtladung der photoelektrisch aufgeladenen Aerosolpartikel
• D. Ermitteln einer Elementarkohlenstoff-Gesamtmenge aus dem mittleren Partikeldurchmesser und aus der Gesamtladung.

A method for determining the total elemental carbon in an aerosol therefore comprises the steps of:

• A. Determining a mean particle diameter of the particles suspended in the aerosol
• B. Photoelectric charging of aerosol particles
• C. Determining a total charge of the photoelectrically charged aerosol particles
• D. Determining an elementary carbon total from the mean particle diameter and from the total charge.

• Der Verfahrensschritt A muss nicht notwendigerweise vor den Verfahrensschritten B und C stattfinden. Vielmehr wird gemäss einem besonders bevorzugten Vorgehen der Verfahrensschritt A in einem ersten und die Verfahrensschritte B und C in einem zweiten Messstrang durchgeführt, wobei von einem zu charakterisierenden Aerosolstrom ein erster Teilstrom durch den ersten und ein zweiter Teilstrom durch den zweiten Messstrang geführt wird.
• Der Verfahrensschritt A wird vorzugsweise mit dem vorstehend beschriebenen Verfahren zur Messung der Anzahlkonzentration und/oder des mittleren Durchmessers von Partikeln durchgeführt. Dies ist aber keine notwendige Voraussetzung. Vielmehr kann der Verfahrensschritt auch mit irgend einem anderen bekannten oder noch zu entwickelnden Verfahren für die Bestimmung einer mittleren Partikelgrösse durchgeführt werden.

The following applies:

• The method step A does not necessarily take place before the method steps B and C. Rather, according to a particularly preferred procedure, the method step A is carried out in a first and the process steps B and C in a second measuring strand, wherein a first partial stream is passed through the second measuring strand of an aerosol stream to be characterized by the first and a second partial stream.
• Process step A is preferably carried out by the method described above for measuring the number concentration and / or the mean diameter of particles. But this is not a necessary requirement. Rather, the method step can also be carried out with any other known or yet to be developed method for the determination of an average particle size.

A relation between particle size, photoelectric charge and total elemental carbon can be determined beispielsiwese by a known amount of elemental carbon in particulate form and suspended in a carrier gas, whereupon the above-mentioned process steps AC are performed in a first step. This is repeated for different particle sizes. Such measurements may be supplemented by other particle characterization methods. The function M = M ( PE, d ) resulting from a number of measurements ( M = total elementary carbon amount, for example in μg, PE = photoelectric charge, d = average particle diameter) depends on the configuration of the photoelectric charger. However, it can be approximated by M = cM _univ , where M _{univ is} a general function once determined and c is an instrument-dependent calibration factor.

A device according to the invention has a gas-conducting arrangement in which an aerosol flows through the diffusion charger and then at least part of it passes through the diffusion separator. A possible Influenzstrommesseinrichtung is upstream or downstream of the diffusion separator in the flow direction, a possible filter for measuring the total charge is connected downstream of both the diffusion and the Influenzsstrommesseinrichtung. As mentioned, as an alternative to this serial arrangement, a parallel arrangement may be used in which the aerosol is in different strands one of which has the diffusion separator and at least one other, for example, the influence current measuring device and / or the filter for the total current measurement. The device may also have conveying means, for example a pump, by means of which the aerosol flow is effected and regulated. Alternatively, the promotion can also be effected by external means, for example in an exhaust gas measurement by the flow generated by the engine.

• Fig. 1 einen Diffusionsauflader einer erfindungsgemässen Vorrichtung,
• Fig. 2 einen Diffusionsabscheider einer erfindungsgemässen Vorrichtung,
• Fig. 3 eine Messanordnung zur Messung des Influenzstromes,
• Fig. 4 eine Messanordnung zur Messung des Gesamtstroms, d.h. der Gesamtladung pro Zeiteinheit,
• Fig. 5 ein Gesamtschema,
• Fig. 6 eine Messanordnung zur Messung der Gesamtkohlenstoff-Menge,
• Fig. 7 eine bevorzugte Ausführungsform der Messanordnung gemäss Fig. 7.

In the following, embodiments of the invention will be described in more detail with reference to figures. In the figures, which are all schematic, show:

• 1 shows a diffusion charger of a device according to the invention,
• 2 shows a diffusion separator of a device according to the invention,
• 3 shows a measuring arrangement for measuring the Influenzstromes,
• 4 shows a measuring arrangement for measuring the total current, ie the total charge per unit time,
• 5 is an overall scheme,
• 6 shows a measuring arrangement for measuring the total amount of carbon,
• 7 shows a preferred embodiment of the measuring arrangement according to FIG. 7.

The charging can be done by ions generated by an electric corona discharge. One possible configuration of a supercharger 10 is shown in FIG. In a cylindrical housing 11 with an aerosol inlet 19 and an aerosol outlet 112 is axially disposed a thin wire 12 to which a high voltage 13 is applied which is large enough to produce a silent electrical discharge (corona) on the wire. A grid arrangement 14 electrically shields the area in which the high-voltage field prevails from the volume 15 through which the aerosol flows. The number of ions passing through the grid into the space 15 can be varied by a small voltage applied to this grid (by a voltage source 16) and measured by an ammeter 17 at an external electrode 18 surrounding the volume through which the aerosol flows. By selecting the voltage applied to the grid 16, the efficiency of the charging can be determined. For the application described, it should be as high as possible, but the tension must not be too high, otherwise charged particles will also be deposited in the supercharger. Typically, it is between 5 V and 30 V. At the output of the supercharger, ions not attached to particles, which could falsify the measurement, are separated by an ion trap. This may be a rod 110 which is connected via a feed 111 to a voltage which is high enough to deposit the ions. Due to the lower mobility, charged particles are not attached to the rod at a measurement-influencing percentage, given a suitable choice of the electrical potential of the rod.

The diffusion separator 20 according to FIG. 2 can be designed as a plate pack 23, which is mounted insulated in an enclosure 21 (plate shut-off) via an insulator 22. With an ammeter 24, the current caused by the charged particles deposited on the plates can be measured. Instead of the disk pack, various other possible solutions are possible. The diffusion separator can also be designed, for example, as a tube package (tube separator) or as a honeycomb structure. Also arrangements of one or more Grids (grid separator) can be used. Various types of diffusion separators can be found in the literature.

An arrangement for measuring the Influenzstromes 30 is shown in FIG 3. In a sealed, electrically conductive housing 31, the aerosol flows through an insulated (insulator 32) mounted electrode 33, which is connected to an ammeter 34. The arrangement for measuring the Influenzstroms has, for example. The substantially identical to the diffusion cylindrical (or non-cylindrical) shape and, for example, the same dimensions, of course, the Abscheideflächen (plates, tubes, honeycomb, grid, etc.) are missing. In such a configuration, the amount of particulates deposited on the electrode 33 is small compared to the influential current caused therein by changes in the total particulate charge in transient processes.

The total charge measurement is carried out in a manner known per se according to the principle of the aerosol electrometer. Here, the particles are collected in an electrically isolated filter and the resulting current is measured, as is already done in the above-mentioned sensors. An example of an aerosol electrometer 40 is shown in FIG. 4. In a sealed, electrically conductive housing 41 with an aerosol inlet 46 and an outlet 47, the aerosol particles are collected in a filter 43. The filter is either itself electrically conductive or built into a conductive, flow-permeable housing 45 (Faraday cage). It is insulated (insulator 42) mounted and connected to an ammeter 44. The measured current corresponds to the total charge per unit time.

A possible combination of the subsystems in FIGS. 1-4 is shown in FIG. 5, wherein the reference symbols used in FIGS. 1 to 4 are shown in FIG designate corresponding elements. Subsequent to the diffusion charger 10, the means for measuring the Influenzsstroms 30, the diffusion separator 20 and the aerosol electrometer 40 are arranged in the flow direction in order. Other arrangements are also conceivable, as already mentioned.

In addition to the embodiment described here, many other types are conceivable, such as the invention can be realized. For example, the diffusion charger may be in a different form than described; The prior art, for example, includes many possibilities for realizing a diffusion charger. The electrode for the influence correction need not have substantially the same shape as the diffusion separator but may have any shape that does not involve any appreciable deposition. For example, it may have the form of a coarse grid upstream of the diffusion separator, which in the extreme case only consists of two bars.

In Figure 6, a measuring arrangement is drawn, which allows the determination of the elementary carbon total amount. According to the arrangement, two measuring strands are each supplied with a partial flow of the aerosol stream to be characterized. In the first measuring stream, the aerosol is characterized by a device for measuring an average particle size 50. The average particle size is reproduced as mean particle diameter. In a second measuring strand particles are electrically charged by a photoelectric charger 60 and then their total charge per unit time in an Aersolelektrometer 40 'measured. The photoelectric charger has a UV light source 62 arranged in a charging chamber 61. The average particle size determined in the device 50 and the total charge measured by the aerosol electrometer 40 'are used by an evaluation unit (not shown) to give a value for the total elemental carbon amount determine.

FIG. 7 also shows an embodiment of the measuring arrangement according to FIG. 6, in which the device for measuring the mean particle size 50 according to FIG. 5 is formed. This combination is particularly preferred.

Claims (14)

Method for measuring the number concentration of particles in an aerosol, wherein the aerosol is electrically charged by means of diffusion charging and subsequently the stream, the charged aerosol particles deposited in a single diffusion separator (20), a plurality of electrically connected in parallel or a plurality of parallel flowed through the diffusion separators , Measured and from this a value for the number concentration is determined. A method according to claim 1, characterized in that the charging of the aerosol by means of a unipolar diffusion charger (10). Method according to one of the preceding claims, characterized in that a single diffusion separator (20) is used. Method according to one of the preceding claims, in which the diffusion separator (20) is designed as a plate separator, as a lattice separator, as a tube separator or as a combination of a plate separator, lattice separator and / or tube separator Method according to one of the preceding claims, characterized in that any influential current which possibly occurs in the diffusion separator (20) is compensated for by measuring an influence current in an additional electrode (33) and this measured value being offset with that of the diffusion separator. A method according to claim 5, characterized in that the geometric shape of the additional electrode corresponds to the geometric shape of the diffusion separator without Abscheideflächen. A method according to claim 5 or 6, characterized in that the diffusion separator (20) and the additional electrode (33) are present in a serial arrangement and are flowed through in succession. Method according to one of the preceding claims, characterized in that in addition to the current in the diffusion separator (20), a total current of the diffusion-charged aerosol is measured and determined from this total current and the current in the diffusion separator, the average diameter of the particles. A method according to claim 8, characterized in that in a separate measuring strand in addition particles of the aerosol are photoelectrically charged, determines the photoelectric charge and from this and the average particle diameter is calculated a total amount of elementary carbon. Method according to one of the preceding claims, characterized in that the number concentration is determined by the current in the diffusion separator multiplied by a calibration factor and optionally corrected by means of measurements of the Influenzstroms and / or the total current correction values. Apparatus for measuring the number concentration and / or the mean diameter of particles of an aerosol, in particular for carrying out the method according to one of the preceding claims, comprising a gas-conducting arrangement in which a flow direction is defined, a diffusion charger (10) and a diffusion separator (20 ), which are arranged so in the flow direction through flowing aerosol first the diffusion charger then at least a portion thereof flows through the diffusion, a current measuring device for determining a diffusion separator in the accumulation of charged particles of the aerosol generated diffusion separation stream, and evaluation means for determining a number concentration from the diffusion deposition stream. Device according to claim 11, characterized in that, characterized by a spatially separated from the diffusion separator additional electrode (33) and an additional power measuring means for measuring the Influenzsstroms generated in the auxiliary electrode. Apparatus according to claim 11 or 12, characterized by an aerosol electrometer (40) for measuring a total flow. Apparatus according to claim 13, characterized in that said gas-conducting arrangement forms a first measuring strand, that a second measuring strand connected in parallel to the first measuring strand is present, which has a photoelectric charger (60) and a device for determining the total charge (40 ') , and further comprising an evaluation device, in which means for calculating an elementary carbon total amount are formed of an average particle size and the photoelectric charge.

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